This research report investigated the ruthenium-catalyzed hydrogenation of aqueous sodium bicarbonate. Subjects of the investigation included: the "blank" effect of the 316 stainless steel reactor in the batch mode; the catalytic activities at 150°C for unsupported ruthenium, including ruthenium purge and the metal produced from the in situ reduction of RuCl3·1-3H2O and Ru(IV)O2·H2O; the catalytic activities at 150°C for supported ruthenium including 4.05% w/w ruthenium on alumina, 5.25 and 20.85%w/w ruthenium on molecular sieve SK-41 (ammonium - substituted Y-type), 3.34 and 17.48% w/w ruthenium on SK-41 (prepared by the in situ reduction of the RuCl3·1-3H2O exchange sieve); orders of reaction rate with respect to hydrogen, bicarbonate, and catalyst at 150°C; activity as a function of temperature; and susceptibility to deactivation. The reaction appears to be zero order in both hydrogen and bicarbonate and first order in catalyst at 150°C in the concentration ranges examined; saturation of an assumed limited number of active catalyst sites is assumed to cause the observed zero orders. Conversion was negligible below 150°C, and optimum in the 150°C-200°C range, with product distribution at 150°C heavily favoring methane; e.g. 99% v/v. The stainless steel reactor was found not to catalyze the reaction at 150°C during a two hour reaction. Catalytic activity for unsupported ruthenium paralleled metal surface area (as determined by BET adsorption), while the inverse was found to be true for sieve-supported metal; mass transfer impedance and electronic effects are assumed to be contributing factors. The reaction on alumina-supported ruthenium produced an undesirable white coating, composition as yet undetermined, which strongly adhered to the support and to the reactor walls. Although the reaction investigated is even more exothermic than the Fischer-Tropsch production of methane, and the ruthenium catalyst was also found to be subject to deactivation, the reaction of interest may have an economic advantage over the Fischer-Tropsch synthesis, in that it is less expensive to decompose a bicarbonate species using hydration energy and then hydrogenate directly, then to thermally decompose the ore and hydrogenate the CO2 produced.
| Identifer | oai:union.ndltd.org:ucf.edu/oai:stars.library.ucf.edu:rtd-1472 |
| Date | 01 January 1980 |
| Creators | Covino, Duane P. |
| Publisher | University of Central Florida |
| Source Sets | University of Central Florida |
| Language | English |
| Detected Language | English |
| Type | text |
| Format | application/pdf |
| Source | Retrospective Theses and Dissertations |
| Rights | Public Domain |
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